Laundry prespotter composition

ABSTRACT

LAUNDRY PRESPOTTER FREE OF WATER AND APPLICABLE TO DAMPENED FABRICS WITHOUT GELLING CONSISTING ESSENTIALLY OF A LIQUID NONIONIC DETERGENT, AN ORGANIC LIQUID MISCIBLE THEREWITH SELECTED FROM CERTAIN ALCOHOLS, ALKYLENE GLYCOLS, ALKYLENE GLYCOL ALKYL OR PHENYL ETHERS, ALKYLENE GLYCOL ESTERS, ALKOXY ETHANOLS AND PROPANOLS AND ALKOXY TRIGLYCOLS, AND OPTIONALLY, AN ENZYME INGREDIENT COMPRISING ALKALINE OR NEUTRAL PROTEASE OR AMYLASE, THE PRESPOTTER CAN BE PACKAGED IN AN AEROSOL CONTAINER FOR USER CONVENIENCE.

Unitcd States Patent 3,741,902 LAUNDRY PRESPOTTER COMPOSITION John H.Barrett, In, Norwalk, Calif., assignor to Purex Corporation, Ltd.,Lakewood, Calif. No Drawing. Filed May 24, 1971, Ser. No. 146,547

Int. Cl. C1111 7/42 US. Cl. 252-90 9 Claims ABSTRACT OF THE DISCLOSUREBACKGROUND OF THE INVENTION This invention has to do with laundryprespotters and more particularly to liquid laundry products useful forprespotting of clothes, prior to regular washing thereof. As such, theinvention is concerned with provision of a laundry prespotter which iseffective in use, .low in cost and liquid for easy application, e.g. byspray or aerosol delivery.

Prior art Laundry prespotters are known. Typically a liquid detergentmay be recommended for application directly onto heavily soiled areas.In other cases, a detergent containing powder may be applied as aconcentrated solution in water to spots expected to be difficult toremove in a normal wash cycle. Enzyme containing prespotters have beenmarketed, in powder form typically, and are highly effective againstprotein based soil, e.g. blood stain. Such products are necessarily dryuntil used because .the enzymes used, protease and amylase, tend to beself-destructive in aqueous environments. See US. Pat. 3,472,783 toSmille et al.; US. Pat. 3,451,935 to Roald et al.; and US. Pat.3,519,379 to Blomeyer et al.

Liquid prespotters relying on detergents for cleansing power haveencountered the problem of gelling of the liquid detergent on mixingwith water. A gelled prespotter is not highly effective.

SUMMARY OF THE INVENTION Accordingly, it is a major objective of thepresent invention to provide a laundry prespotter containing a liquiddetergent which is non-gelling on admixture with water in use and whichas well is a suitable environment for enzymes and amenable toconvenience packaging, e.g. in aerosol containers. y

This and other objectives of the invention, to become apparenthereinafter, are realized in a laundry prespotter according to theinvention which consists essentially of a mixture free of water andglycerine and containing per 100 parts by weight from to 20 parts of aliquid nonionic detergent and an organic liquid miscible therewith in anamount sufiicient to prevent gelling of the detergent on water contactbetween 95 and 20 parts selected from certain alcohols, alkyleneglycols, alkylene glycol ethers and esters, alkoxy ethanols andpropanols, ketones and alkoxy triglycols. The mixture is a favorableenvironment for protease and amylase enzyme, e.g. in weightconcentrations of 0.05 to 5% of the'mixture, where the mixture is freeof organic solvents for the enzymes, hereinafter enumerated. Infact,s'uch-'mixtures have been de'mQn- 3,741,902 Patented June 26, 1973strated stable, i.e. efficacious for periods over one year when storedat F. The mixture with or without the enzyme may be aerosol packagedwith suitable propellant, particularly for foamed application topremoistened soil on fabric.

Thus, the invention provides as well method of maintaining ungelled aliquid nonionic detergent which is sprayed onto a water wet surface,e.g. of fabric, which includes coapplying to the surface with thedetergent an organic liquid miscible with the detergent as identifiedherein. In aerosol delivery applications, the method further includesdissolving a normally gaseous but liquefiable propellant in the mixtureunder pressure in an aerosol dispensing can in an amount between 1 and5% by weight of the mixture, to foam the coapplied components of themixture upon application to the surface.

DESCRIPTION OF THE PREFERRED EMBODIMENTS As indicated, the presentinvention is concerned with improved gelation behavior in liquidnonionic detergents which enables their use effectively as prespotters.This result is achieved in water free mixtures of liquid nonionicdetergents and organic liquids miscible therewith.

The term nonionic detergent herein includes those produced by theintroductionof alkylene oxide group into an organic hydrophobic compoundor group having an aliphatic or aromatic structure. The hydrophobicorganic group generally contains at least 8 carbon atoms and up to about30 carbon atoms. Condensed with the hydrophobic group are at least 5 andpreferably up to about 50 alkylene oxide groups. It is preferred to usethe polyoxyethylene condensates derived from ethylene oxide. It ispreferred to use the polyalkylene oxide condensates of alkyl phenol,such as the polyoxyethylene ethers or alkyl phenols having an alkylgroup of at least about six, and usually about 8 to 12 carbons, and anethylene oxide ratio (No. of moles per phenol) of about 7.5, 8.5, 11.5or 20, though the number of ethylene oxide groups will be usually fromabout 8 to 18. The alkyl substituent on the aromatic nucleus may bedi-isobutylene, diamyl, polymerized propylene, dimerized C -C olefin,and the like.

Further suitable nonionic detergents are the polyoxyalkylene esters oforganic acids, such as the higher fatty acids, rosin acids, tall oilacids, or acids from the oxidation of petroleum, et cetera. Thesepolyglycol esters will contain usually from about 12 to about 30 molesof ethylene oxide or its equivalent and about 8 to 22 carbons in theacyl group. Suitable products are refined tall oil condensed with 16 or20 ethylene oxide groups, or similar polyglycol esters of lauric,stearic, oleic acids, etc.

Additional nonionic detergents are the polyalkylene oxide condensateswith higher fatty acid amides, such as the higher fatty acid primaryamides, monoand diethanolamides. Suitable agents are coconut acid fattyamide condensed with about 10 to 50 moles of ethylene oxide. The fattyacyl group will have similarly about 8 to 22 carbons, and usually about10 to 18 carbon atoms,

in such products. The corresponding sulfonamides may be used also ifdesired.

Other suitable polyether nonionic detergents are the polyalkylene oxideethers of high aliphatic alcohols. Suitable fatty alcohols having ahydrophobic character, preferably 8 to 22 carbons, are lauryl, myristyl,cetyl, stearyl and oleyl alcohols which may be condensed with anappropriate amount of ethylene oxide, such as at least about 6, andpreferably about 10 to 30 moles. A typical product is' oleyl alcoholcondensed with about 12, 15 or 20 moles of ethylene oxide. Thecorresponding higher alkyl mercaptans or thioalcohols condensed withethylene oxide are suitable in the present invention also. Thewater-soluble polyoxyethylene condensates withhydrophobic'polyoxypropylene glycols may be employed also.

Further suitable nonionic detergents are the higher fatty acidalkanolamides, such as the monoethanolamides, diethanolamides andisopropanolamides wherein the acyl radical has about to 14 carbon atomsand amine oxides.

Examples are coconut (or equivalent lauric), capric and myristicdiethanolamide, monoethanolamide and isopropanolamide, dodecyl dimethylamine oxide and dimethyl acetoxyalkylamine oxide where alkyl is C -CIntimately mixed with the above mentioned detergents are organic liquidsmiscible therewith. Suitable co-liquids include:

(1) Alcohols having 1 to 13 carbon atoms, e.g. alcohols selected frommethanol, ethanol, propanols, butanols, pentanols, hexanols, heptanols,iso-octanols, iso-decanols, trimethyl-4-nonanol and tridecanol;

(2) Alkylene glycols having molecular weights up to 600, e.g. selectedfrom ethylene glycol, diethylene glycol, triethylene glycol, propyleneglycol, dipropylene glycol, hexylene glycol, polyethylene glycols havingmolecular weights between 190 and 600, 2-methyl-2-ethyl-1,3 propanediol,2-ethyl-1,3-hexanediol, and tetraethylene glycol;

(3) Alkylene glycol alkyl or phenyl ethers, e.g. having molecularweights up to 207 in which the alkyl group or phenyl group contains upto 6 carbon atoms. Among others these ethers may be mentioned:diethylene glycol diethyl ether, diethylene glycol monomethyl ether,diethylene glycol dibutyl ether, diethylene glycol monobutyl ether,propylene glycol monomethyl ether, and dipropylene glycol monomethylether;

(4) Ethylene glycol alkyl esters having molecular weights up to 205, inwhich the ester group contains from 2 to 4 carbon atoms inclusive, e.g.diethylene glycol monomethyl ether acetate, and diethylene glycolmonobutyl ether acetate;

(5) Alkoxy ethanol or propanols having a molecular weight up to 201 andin which the alkoxy group contains up to 4 carbon atoms, e.g.2-ethoxyethanol, methyl-2- ethoxyethanol, isobutyl-2-ethoxyethanol,butyl-2-ethoxyethanol, hexyl-Z-ethoxyethanol, phenyl-Z-ethoxyethanol,l-butoxyethoxy-Z-propanol, n-butoxy 2 propanol and n-propoxy-Z-propanol;

(6) Ketones having a molecular weight up to 185, e.g. selected from thegroup consisting of acetone, methylethyl ketone, methylisobutyl ketone,cyclohexanone, methyl-n-amyl ketone, methylisoamyl ketone, ethylbutylketone, diisobutyl ketone, 'isobutylheptyl ketone, mesityl oxide,isophorone, acetyl acetone and diacetone alcohol; and

(7) Alkoxy triglycols having a molecular weight up. to 207 and in whichthe alkoxy group contains up to 4 carbon atoms inclusive, e.g. selectedfrom methoxytriglycol, ethoxytriglycol and butoxytriglycol.

The laundry prespotter typically employs the mentioned nonionicdetergents and organic liquids in proportions per 100 parts by weight oftheir mixture of 5 to 80 parts of detergent and correspondingly to 95parts of the organic liquid. In preferred formulations at least 40 partsby weight of detergent is employed.

The above mixture may also include a thickening agent,

e.g. from 0.25 to 10% by weight of a polyethylene glycol having amolecular weight between 1000 and 20,000.

The described compositions form highly desirable vehicles for enzymes tobe used as prespotters. Suitable enzymes are described in detail in U.S.Pat. 3,451,935 above mentioned, which is hereby incorporated byreference.

Particularly preferred are neutral or alkaline protease i and amylaseenzymes, suitably having an average particle size of from 1 to 100microns. Amounts of enzymes employed may range between 0.05 and 5percent by weight,

or higher if economics permit, e.g. to 15%,-by weight based on theweight of the mixture of detergent and organic liquid. Solvents forenzyme ingredients should be excluded from the formulations. thus,water, glycerine,

ethylene'glycol, diethylene-glycol, triethylene glycol, propylene glycoland dipropylene glycol liquids are not to be used in enzyme compositionsaccording to the invention. Thickening agents such as those mentionedabove may be used in the enzyme versions of the invention compositions,and in the above-mentioned amounts. While pH of the enzyme prespotter isnot narrowly critical, it is desirablyon the near to neutral to alkalineside, i.e. between 6 and 10.

, The just described compositions are liquid and highly adapted to sprayapplication onto premoistened spots on fabric. Local, application thuslymeans economy 1n use. Alternatively the prespotter may be poured ontospotted areas oradded to water for soaking or incorporated 1n wash waterin a conventional washing machine.

Maximum benefit is realized through spray application, e.g. by pumpingthrough a nozzle or preferably by aerosol spray application.

In a highly preferred embodiment, there is provided an aerosol packagecomprising a pressure resistant can having a dispensing nozzle andcontaining the nomomc detergent-organic liquid mixture or the nonionicorganic liquid-enzyme mixtures mentioned, as well as a conventionalaerosol propellant, e.g. nitrogen, carbon dioxide, nitrous oxide, aninert hydrocarbon having up to five carbon atoms or halogenatedhydrocarbon having up to four carbon atoms, which is normally gaseous,but liquefiable at container pressure below 75 pounds/square inch gaugeat 25 C., and preferably one which is at least partially soluble in themixtures mentioned in an amount suflicient to cause foaming of theliquid on discharge from the container through the nozzle, e.g. solubleenough to form 1% to 50% solutions in the liquid mixture.

EXAMPLES In the examples following all parts and percentages are byweight unless otherwise indicated.

Enzyme I herein i s a blend of neutral and alkaline proteaseandi-amylase sold by Monsanto Company under the name Enzyme AP.

Enzyme II herein is a blend of alkaline protease and -amylase sold byRohm and Haas Company under the name Protease 57.

Enzyme III is a blend of alkaline protease and amylase 7 moles ofethylene oxide (Neodol 25-7) Deter-gent E is anonyl phenoxy poly(ethyleneoxy) ethanol (Igepal C0630).

Example 1 A prespotter composition was prepared by blending 0.5 part ofEnzyme I, 49 parts of hexylene glycol, 49 parts of Detergent B and 1.5.parts of Polyethylene Glycol 6000. Even after threemonths of storage atF., the composition effectively removed blood and carbohydrate stainsfrom test cloths as well as grease and ball point pen ink stainstherefrom.

Example 2 Example 1 .was duplicated using 65 parts of Detergent B and33. parts of Glycol 6000. The composition was similarly.effecti-ve as astain remover and prespotter before and after storage. 1 a

' Example 3 Example 1 wasduplicated using 59.5, parts of Detergent C, 40parts of dioxane as the organic liquid, and omitting the Glycol 6000.The composition was similarly effective as a stain remover andprespotter before and after storage.

Example 4 An aerosol package was made up by packaging under pressure ina dispensing container. Enzyme I, 0.25 part, Detergent A, 52.65 parts,hexylene glycol 26.35 parts, Polyethylene Glycol 6000, 0.5 part, Freon12 (dichlorodifluoromethane), 20 parts, and perfume 0.25 part. Thecomposition is elfective as a prespotter sprayed directly onto areas ofcloths previously stained with blood, spinach, starch, grease and ballpoint pen ink. The composition was tested again after 13 months ofstorage at 130 F. and again found efiective.

Example 5 Example 4 was duplicated substituting Detergent D forDetergent A. The composition was similarly effective and stable.

Example 6 Example 4 was duplicated substituting Detergent E forDetergent A. The composition was similarly elfective and stable.

Example 7 A non-gelling nonionic prespotter composition free of enzymewas prepared using Detergent C, 50 parts, and dioxane, 50 parts. Thecomposition was an efiective prespotter against grease and ball pointpen ink, but not as effective against protein stain as the precedingexamples.

Example 8 Example 7 was duplicated substituting hexylene glycol fordioxane. The composition was similarly effective as the prespotter inExample 7 and non-gelling.

Example 9 Example 7 was duplicated substituting propoxy propanol fordioxane. The composition was similarly eifective as the prespotter inExample 7 and non-gelling.

Example 10 Example 7 was duplicated using Detergent E for Detergent Cand mesityl oxide for the dioxane. The composition was similarlyeffective as the prespotter in Example 7 and non-gelling.

Example 11 Test cloths were written upon with ball point pens and greasestained. The fabric was moistened with water and treated with thecomposition of Example I, delivered from an aerosol dispenser. The inkand grease stains were offectively removed. Similar effectivenessagainst premoistened protein and carbohydrate soil was also found. Nogelling of the applied detergent was noted in the tests.

Example 12 A liquid mixture containing 0.5% Enzyme I, and 99.5 parts ofa 60:40 mixture of a detergent (Tergitol 45-8-10) and dioxane was addedto a washing machine load comprising blood and carbohydrate soiled testcloths at a level of 0.25 cup/ 60 liters of wash water (ca. 0.10% byweight) and effectively removed the indicated soil.

Control I Detergent A is sprayed onto moistened cloth containing testsoil specimens of blood and chocolate. The detergent gells and does notremove the stain or facilitate its removal in a normal washing cycle.

Control II Example 1 is duplicated substituting ethylene glycol forhexylene glycol. The solution is evaluated for stain removal every day.After seven days storage at 70 F. the enzyme dropped to one-third itsoriginal removal rate.

Example 13 Example 1 is duplicated substituting a coconut fatty acidamide condensed with 10 moles of ethylene oxide for Detergent A. Thecomposition is an effective prespotter.

Example 14 Example 1 is duplicated substituting oleyl alcohol condensedwith 15 moles of ethylene oxide for Detergent A. The composition is aneffective prespotter.

Example 15 organic liquid miscible therewith in an amount sufficient' toprevent gelling of the detergent on water contact between and 20 parts,said organic liquid being selected from the group consisting of alcoholshaving 1 to 13 carbon atoms selected from the group consisting ofmethanol, ethanol, propanols, butanols, pentanols, hexanols, heptanols,iso-octanols, iso-decanols, trimethyl-4- nonanol, and tridecanol;alkylene glycols having molecular weights up to 600 selected from thegroup consisting of ethylene glycol, diethylene glycol, triethyleneglycol, propylene glycol, dipropylene glycol, hexylene glycol,polyethylene glycols having molecular weights between about 190 and 600,2-methyl-2-ethyl 1,3-propanediol, 2- ethyl-l, 3-hexanediol, andtetraethylene glycol; alkylene glycol alkyl ether selected from thegroup consisting of diethylene glycol diethyl ether, diethylene glycolmonomethyl ether, diethylene glycol dibutyl ether, diethylene glycolmonobutyl ether, diethylene glycol monophenyl ether, propylene glycolmonomethyl ether and dipropylene glycol monomethyl ether; or ph'enylethers having molecular weights up to 207, alkylene glycol alkyl estershaving molecular weights up to 205, selected from the group consistingof diethylene glycol monoethyl ether acetate and diethylene glycolmonobutyl ether acetate; alkoxy ethanols and alkoxy propanols havingmolecular weights up to 201 selected from the group consisting of 2ethoxyethanol, methyl 2 ethoxyethanol, isobutyl-2- ethoxyethanol, butyl2 ethoxyethanol, hexyl-Z-ethoxyethanol, phenyl-Z-ethoxyethanol,l-butoxyethoxy-2-propanol, n-butoxy-2-propanol and n-propoxy-2-propanol;ketones having molecular weights up to 185 selected from the groupconsisting of acetone, methylethyl ketone, methylpropyl ketone,methylisobutyl ketone, cyclohexanone, methyl-n-amyl ketone,methylisoamyl ketone, ethylbutyl ketone, diisobutyl ketone,isobutylheptyl ketone, mesityl oxide, isophorone, acetyl acetone anddiacetone alcohol; and alkoxy triglycols having molecular weights up to207 selected from the group consisting of methoxytriglycol,ethoxytriglycol and butoxytriglycol.

2. Prespotter according to claim 1 including also from 0.25 to 10% byweight based on the weight of the mixture of a polyethylene glycolhaving a molecular weight between 1000 and 20,000 as a thickening agent.

3. Prespotter according to claim 1 including also from 0.05 to 5 percentby weight of a solid, particulate enzyme selected from the groupconsisting of alkaline protease, neutral protease and amylase, based onthe weight of nonionic detergent and organic liquid combined, with theproviso that said prespotter is additionally free of ethylene glycol,diethylene glycol, triethylene glycol, propylene glycol and dipropyleneglycol solvents for the enzyme.

4. Prespotter according to claim 3 in which said enzymes have an averageparticle size of from 1 to microns.

5. Prespotter according to claim 3 in which said prespotter has a pHbetween 6 and 10.

6. Prespotter according to claim 3 including also from 0.25 to by weightbased on the weight of the mixture of a polyethylene glycol having amolecular weight between 1000 and 20,000, as a thickening agent.

7. Aerosol package comprising a pressure resistant can having adispensing nozzle and containing the laundry prespotter defined in claim1 and a propellent for dispensing the same, said propellant comprising anormally gaseous but liquefiable material at least partially soluble inthe mixture in an amount sufficient to cause foaming of the prespotterliquid on discharge from the container through said nozzle.

8. Aerosol package comprising a pressure resistant can having adispensing nozzle and containing the laundry prespotter defined in claim3 and a propellant for dispensing the same, said propellant comprising anormally gaseous but lique fiable material at least partially soluble inthe mixture in an amount suflicient to cause foaming of the prespotterliquid on discharge from the container through said nozzle.

9. Aerosol package comprising a pressure resistant References CitedUNITED STATES PATENTS 3,625,909 12/1971 Berg ct a1. 252-171 3,627,68812/19'7l McCarty et al. 252'DIG. 12 3,557,002 1/197 1' McCarty 252-DIG.12 3,635,828 1/1972 Benjamin et al. 252-DIG. 12 3,131,153 4/1964Klausner 252.

WILLIAM E. 'SCHULZ, Primary Examiner US. Cl. X.R.

8142; -63; 252-471, DIG. 12

